Download PDF
Synlett 2010(12): 1833-1836  
DOI: 10.1055/s-0030-1258093
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Double α-Addition Reaction of ortho-Hydroxyacetophenones to Ethyl Propiolates Mediated by Ph3P: Synthesis of Functionalized 1,4-Pentadienes

Ling-Guo Mengb, Kai Tangb, Hui-Fang Liua, Jiang Xiaoa, Song Xue*a
a Department of Applied Chemistry, Tianjin University of Technology, Tianjin 300191, P. R. of China
Fax: +86(22)60214252; e-Mail: xuesong@ustc.edu.cn;
b Department of Chemistry, University of Science and Technology of China, Hefei 230026, P. R. of China
Further Information

Publication History

Received 9 April 2010
Publication Date:
14 June 2010 (online)

    Permissions and Reprints All articles of this category

Abstract

A new way of synthesizing functionalized 1,4-pentadienes by double α-addition reaction of ortho-hydroxyaceto­phenones to ethyl propiolate mediated by Ph3P in moderate yields is described. On the other hand, other ortho-hydroxyphenyl ketones resulted in the single α-addition products in moderate to good yields.

Key words

α-addition - functionalized 1,4-pentadienes - Ph3P - ortho-acylphenols - ethyl propiolates

    References and Notes

  • 1a Eilbracht P. Acker M. Totzauer W. Chem. Ber.  1983,  116:  238 
    Google Scholar
  • 1b Denmark SE. Guagnano V. Dixon JA. Stolle A. J. Org. Chem.  1997,  62:  4610 
    Google Scholar
  • 1c Grigg R. Dorrity MJ. Heaney F. Malone JF. Rajviroongit S. Sridharan V. Surendrakumar S. Tetrahedron  1991,  47:  8297 
    Google Scholar
  • 1d Roulet J.-M. Deguin B. Vogel P. J. Am. Chem. Soc.  1994,  116:  3639 
    Google Scholar
  • 1e Prasad ASB. Knochel P. Tetrahedron  1997,  53:  16711 
    Google Scholar
  • 2a Nicolaou KC. Ramphal JY. Petasis NA. Serhan CN. Angew. Chem., Int. Ed. Engl.  1991,  30:  1100 
    Google Scholar
  • 2b Durand S. Parrain J.-L. Santelli M. J. Chem. Soc., Perkin Trans. 1  2000,  253 
    Google Scholar
  • 2c Andrey O. Glanzmann C. Landais Y. Parra-Rapado L. Tetrahedron  1997,  53:  2835 
    Google Scholar
  • 3a Matsuhashi H. Hatanaka Y. Kuroboshi M. Hiyama T. Tetrahedron Lett.  1995,  36:  1539 
    Google Scholar
  • 3b Matsushita H. Negishi E. J. Am. Chem. Soc.  1981,  103:  2882 
    Google Scholar
  • 3c Agrios KA. Srebnik M. J. Org. Chem.  1994,  59:  5468 
    Google Scholar
  • 3d Klaps E. Schmid W. J. Org. Chem.  1999,  64:  7537 
    Google Scholar
  • 3e Hara R. Nishihara Y. Landré PD. Takahashi T. Tetrahedron Lett.  1997,  38:  447 
    Google Scholar
  • 4a Basavaiah D. Kumaragurubaran N. Sharada DS. Tetrahedron Lett.  2001,  42:  85 
    Google Scholar
  • 4b Basavaiah D. Sharada DS. Kumaragurubaran N. Reddy RM. J. Org. Chem.  2002,  67:  7135 
    Google Scholar
  • For review, see:
  • 5a Lu X. Zhang C. Xu Z. Acc. Chem. Res.  2001,  34:  535 
    Google Scholar
  • 5b Valentine DH. Hillhouse JH. Synthesis  2003,  317 
    Google Scholar
  • 5c Methot JL. Roush WR. Adv. Synth. Catal.  2004,  346:  1035 
    Google Scholar
  • 5d Ye L.-W. Zhou J. Tang Y. Chem. Soc. Rev.  2008,  37:  1140 
    Google Scholar
  • 5e Nair V. Menon RS. Sreekanth AR. Abhilash N. Biju AT. Acc. Chem. Res.  2006,  39:  520 
    Google Scholar
  • 6a Trost BM. Dake GR. J. Am. Chem. Soc.  1997,  119:  7595 
    Google Scholar
  • 6b Meunier S. Siaugue J.-M. Sawichi M. Calbour F. Dézard S. Taran F. Mioskowski C. J. Comb. Chem.  2003,  5:  201 
    Google Scholar
  • 6c Hanédanian M. Loreau O. Taran F. Mioskowski C. Tetrahedron Lett.  2004,  45:  7035 
    Google Scholar
  • 6d Hanédanian M. Loreau O. Sawicki M. Taran F. Tetrahedron  2005,  61:  2287 
    Google Scholar
  • 7a Xue S. Zhou Q.-F. Zheng X.-Q. Synth. Commun.  2005,  35:  3027 
    Google Scholar
  • 7b Meng L.-G. Tang K. Guo Q.-X. Xue S. Tetrahedron Lett.  2008,  49:  3885 
    Google Scholar
  • 8 Meng L.-G. Hu B. Wu Q.-P. Liang M. Xue S. Chem. Commun.  2009,  6089 
    CrossrefGoogle Scholar
9

General Reaction Procedure
To a solution of ortho-acylphenols (0.6 mmol) with terminal alkynoates (0.6 mmol) in dry CH2Cl2 (2 mL) was added Ph3P (79 mg, 0.3 mmol), and the resulting mixture was stirred at r.t. for 16 h. The solvent was removed in vacuo, and the residue was purified by column chromatography on silica gel (PE-EtOAc = 20:1) to give the desired product.